Phosphorus-free detergent formulation

ABSTRACT

Certain salts of water-soluble terpolymers derived from allyl alcohol, sulfur dioxide and acrylic or methacrylic acid have been found useful replacements for phosphorus-containing compounds in detergent formulations containing various surfactants.

United States Patent 252/554, 555, 558, DlG. 2, DIG. l5

McGuire May 13, 1975 PHOSPHORUS-FREE DETERGENT [56] References Cited FORMULATION UNITED STATES PATENTS [75] Inventor: Stephen E. McGuire, Ponca City. 2,794.0!4 5/l957 Dreisbach et al 260/793 A Okla, 3,308,067 3Il967 Diehl 252/558 X l 0 3,692,704 9/l972 Stamm et al .7 252/558 X 1 Asslgneei cflnlllwml Company, Ponca 3.706.672 :2/1972 Martin et al. 252/156 City, Okla. 22 Filed; 9 197 Primary Examiner-Herbert B. Guynn Attorney, Agent, or FirmRonald J. Carlson [2l] Appl. No.: 330,932

[57] ABSTRACT {52] US. Cl. 252/545; 252/526; 252/530; Certain salts f wmepsomble erpdymel-s derived 252/5491 252/550; 252/551; 252/558; from allyl alcohol, sulfur dioxide and acrylic or meth- 252/D|G- 2; ZSZ/DIG- H acrylic acid have been found useful replacements for [Sl] Int. Cl. Clld 1/02; Clld 3/34 phosphorusomaining compounds in detergent 158] Field of Search 252/545, 549, 550, 55l, muhnions containing various Surfactants 4 Claims, I Drawing Figure FEJENTED RAY 1 3195 3.883 ,446

SULPHUR DIOXIDE o o o o O o O o ACRYLIC 0R METHACRYL/C ACID ALL ALCOHOL 1 PHOSPHORUS-FREE DETERGENT FORMULATION This invention relates to nonphosphorus-containing detergent formulations. More particularly, the invention relates to the use of certain water-soluble terpolymer salts as substitutes for phosphorus-containing compounds in detergent formulations.

Phosphorus-containing compounds long used in detergent formulations have recently come under criticism by environmentalists as contributing to the eutrophication of lakes and streams into which such formulations eventually pass as effluent. Enhancement of eutrophication, of course, may lead to excessive vegetative growth in such waterways and result in impairing the natural ecological balance.

While phosphorus-containing compounds have been used to a great extent in detergent formulations it is known that various other compounds may be used in their place such as alkali metal carbonates, borates, silicates, nitriloacetates and amino carboxylates as well as the corresponding ammonium or substituted ammonium salts. Such compounds are disclosed in US. Pat. No. 3,390,094. However, these other compounds have not gained wide acceptance as substitutes for the phosphorus-containing compounds and, thus, researchers continue to seek discovery of other replacements.

In accordance with this invention it has been found that certain watersoluble terpolymer salts may be employed as substitutes for phosphorus-containing compounds in detergent formulations. Detergency evaluations have shown that these water-soluble terpolymer salts perform generally as well as phosphoruscontaining compounds, and particularly with respect to cotton fabrics, in a variety of detergent formulations.

The water-soluble terpolymer salts which have been found suitable as replacements for phosphoruscontaining compounds in detergent formulations are the alkali metal, ammonium, or alkylolammonium salts of terpolym ers derived from acrylic acid or methacrylic acid, sulfur dioxide and allyl alcohol, wherein the proportions of each fall within the shaded area of the diagram shown in the drawing. The terpolymers are known, being fully described in US. Pat. No. 2,794,014, including their preparation. In general, the terpolymers will be derived from about to about 40 percent by weight allyl alcohol, about 1 to about 43 percent by weight sulfur dioxide and about to about 83 percent by weight acrylic or methacrylic acid, provided that the particular proportions fall within the shaded area of the diagram. The terpolymer salts are prepared simply by neutralizing the above terpolymers with the appropriate base desired.

The detergent formulations with which the above described water-soluble terpolymer salts may be used will include surfactants and may include various other additives well-known in detergent formulations. Generally, the surfactants which may be used include the various known detergent sulfonates, sulfates and alkoxylated alcohols, and mixtures thereof, all of which are commercially available. The sulfonates and sulfates are normally in the form of alkali metal, ammonium or alkylolammonium salts, such as sodium; potassium; ammonium; monoethanol; diethanol and triethanol ammonium salts; and tributanol ammonium salts.

The sulfonates, in particular, include alkylbenzene sulfonates, olefin sulfonates and alkane sulfonates. The

preferred alkylbenzene sulfonates are those wherein the alkyl group has about 8 to 20 carbon atoms. The olefin sulfonates are preferably those derived from mono-olefins having about l0 to 24 carbon atoms. Similarly, the alkane sulfonates are preferably those derived from paraffms having about l0 to 24 carbon atoms.

The sulfates include alcohol sulfates (alkanol sulfates), preferably derived from monohydroxy alkanols having about 10 to 24 carbon atoms, and alcohol ether sulfates (alkoxylated alkanol sulfates), preferably derived from monohydroxy alkanols having about 8 to 24 carbon atoms which have been alkoxylated with up to about 80 percent by weight of an alkylene oxide, such as ethylene oxide, with about 5 to 65 percent by weight being further preferred.

The alkoxylated alcohols are preferably those derived from monohydroxy alkanols having about 8 to 24 carbon atoms which have been alkoxylated with about 45 to 80 percent by weight of an alkylene oxide, such as ethylene oxide, with about 60 to percent by weight being further preferred.

in general, the nonphosphorus-containing detergent formulations of the invention will comprise about 0.l to about 25 parts by weight of the previously described terpolymer salts per part by weight of the surfactant. Other conventional additives which do not contain phosphorus may also be used in the formulations such as hydrotropes, foam suppressants, foam boosters, foam stabilizers, additional sequestering agents, sodium sulfates, sodium silicates, and agents for preventing soil redeposition such as alkali carboxymethylcellulose. The formulations may be either liquids or solids such as granules.

The following examples will serve to further illustrate the above-described invention.

EXAMPLE 1 A first sodium salt of a terpolymer designated A of allyl alcohol, acrylic acid and sulfur dioxide was prepared by charging about lSOg of water, about 3g of ammonium persulfate and about 24g of allyl alcohol to a reaction vessel. The mixture was cooled to about l5C and about 50g of acrylic acid was added. The mixture was then further cooled to about 1 5C and about 26g of liquid sulfur dioxide was added. After purging the vessel for about l5 seconds with nitrogen the vessel was sealed and heated to about 40C with stirring to initiate polymerization. Polymerization was continued for about 22 hours whereafter the reaction mixture was vented and about 100g of water were added. About 100 ml of liquid were then distilled from the crude terpolymer reaction product. The terpolymer was then converted to the sodium salt by adding 300 ml water to the reaction product to decrease viscosity followed by addition of an excess of 50% NaOH while allowing the mixture to warm to about 60C. The sodium salt of the terpolymer was then precipitated by adding about 4,500 ml methanol. The white granular salt was filtered and dried and then ball milled to a fine white powder.

A second sodium salt ofa terpolymer designated 8" of allyl alcohol, acrylic acid and sulfur dioxide was prepared in the same manner described above except that 10g of allyl alcohol, g of acrylic acid and 10g of sulfur dioxide were employed as the reactants and the polymerization was carried out at about 40C for about 60 hours. Work-up ofthe terpolymer to obtain the sodium salt in a white powder form was the same.

Detergent formulations of each of the above were then individually prepared by blending 40 parts by The above data indicates that while the effectiveness of the sodium salts of the terpolymers was not quite as great as the sodium tripolyphosphate. they are sufficiently effective as replacements therefor.

weight of the above sodium salt of the terpolymer with 5 about 15 parts by weigth of the sodium sulfonate salt EXAMPLE 2 of C -C alkylbenzene (Nalkylene 600). Other conventional additives included in the formulation were 8 Th di l f a l er of allyl alcohol, Parts y Wfilghl Of a Commemlal Sodium Silicate acrylic acid and sulfur dioxide, identified as "B" above. (Philadelphia QUMWRU 8 2/ 2 as a 10 was compared with sodium tripolyphosphate for detercol'mslcm inhibitor and builder 1 P y Weight of gency effectiveness in another detergent formulation. dlum cafboxl'melhylcellulose as anli'sull redcposi' In each of these formulations 50 parts by weight of eition agent. 26 parts of weight of sodium sulfate as inert the the terpolymu l or h i l h h r was and 10 P y weight molslureused. The surfactant in each formulation included 7.5 A detergency evaluation was made Bach 0f the parts by weight of the sodium sulfonate salt of C -C above formulations by soiling three swatches of each of alkylbenzene (Nalkylene 600) and 9.2 parts by weight )P' of fabric using essentially the tecihl'llquc of the sodium sulfate salt of mixed C and C linear scribed y 1 B et 31 JACS 42 723 primary alcohols. Other ingredients included 3.5 parts of the swatches were tested for Hunter reflectance an by weight lauryl isopropanolamide as a foam stabilizer, then washed in a conventional Terg-O-Tometer using 75 rts by weight of sodium silicate (same as i E water having l50 pp hardness expressed as Cacom a ample l) and 12.3 parts by weight sodium sulfate. temperature of about 120"F, an 0.15 wt% detergent formulation concentration, an agitator speed of 100 Detergency evaluations were made as described in rpm. and a ten-minute wash cycle followed by a five Example 1 with water having 50 ppm hardness and minute rinse cycle. After washing and drying the again with water having 200 ppm hardness and the reswatches were again tested for Hunter reflectance. The Suits are tabulated in Table ll.

TABLE II Detergency (AL) Formulation H Cotton Dacron/Cotton Dacron Average Terpolymer salt 9.0 10.4 1.2 1010 Tripolyphosphate 50 8.8 1 1.6 12.2 10.1

Terpolymcr salt 20a "is 8.4 10.4 8.9

Tripolyphosphate 201) 7.9 10.2 11.3 9.8

water hardness expressed as CaCO "same as defined in Example 1 difference in the Hunter reflectance (AL), before EXAMPLE 3 washing versus after washing, was computed for each swatch and average difference for each type of fabric was computed and recorded.

For comparison, detergent formulations were prepared identical to those above except that in one (designated C) the sodium salt of the terpolymer was omitted without replacement and in the other (designated D) it was replaced with sodium tripolyphosphate in an equal amount. Each of these formulations were evaluated for detergency in the same manner described above on fabric swatches which were soiled in the same manner described above and at the same time.

The results of the detergency evaluations are tabulated in Table l.

The terpolymer salt identified as B in Example 1 was further evaluated with other surfactants in various formulations, The formulations are described in Table IIlA.

TABLE lllA TABLE 1 Detergency (Ave AL) Formulation Cotton Dacron/Cotton Dacron Average A 10.3 6.7 9,7 8.9 B 12.2 9.3 10.9 10.1 C 4.6 3.2 3.2 3.7 D 12.7 11.3 11.7 11.)

cotton broadcloth (Testl'ubrics 5141918] 65/35 dacronlcotton with permanent press finish (Testt'abries 5/7406 Wit! 1 ducron (Testfahrics 51 541 sodium sulronute salt ufC -C alkylben/ene tNulkylene (still) 60 wtil ethoxylute of C C and C linear alcohols lAlflmic I2 1 8-601 sodium sulfate ufa 4U wr-v ethnxylalc of c linear alcohols [Alfnnic 1412-5) sodium carhuxyrnclhylcellulosc sodium silicate [Philadelphia Uuarv-RU (irude Si(),/Na,0=2.4l

The above formulations were evaluated for detergency as described in Example 2 and the results are tabulated in Table lllB.

TABLE "1B Detcrgency (AL) Form ulution H' Cotton Dacron/Cotton Dacron Average I 50 8.6 10.4 11.6 10.0 11 50 0.0 10.5 12.0 10.1 111 50 8.8 11.0 11.7 10.1 IV 50 8.8 10.4 11.4 10.0 I 200 7.2 7.5 9.2 8.0 ll 200 11.4 8.1 9.6 8.7 III 200 8.6 10.2 10.8 9.9 W 200 11.4 0.8 10.4 3.5

water htllLlm-tllt expressed as (u((),-. same as defined in Example 1 Thus. having described the invention in detail. it will be understood that certain variations and modifications may be made without departing from the spirit and scope of the invention as described herein and in the appended claims.

I claim:

1. A nonphosphorus-containing detergent formulation consisting essentially of a surfactant and an alkali metal, ammonium. or alkylolammonium salt of a watersoluble terpolymer of about to 40 percent by weight allyl alcohol, about 1 to 43 percent by weight sulfur dioxide and about 20 to 83 percent by weight acrylic or methacrylic acid. provided that the particular proportions fall within the shaded area of the diagram on the annexed drawing; said surfactant being a. an alkali metal, ammonium, or alkylolammonium alkylbenzene sulfonate;

b. an alkali metal, ammonium, or alkylolammonium olefin sulfonate;

c. an alkali metal, ammonium, or alkylolammonium I alkylsulfonate;

d. an alkali metal, ammonium, or alkylolammonium alkanol sulfate;

e. an alkali metal, ammonium, or alkylolammonium alkoxylated alkanol sulfate;

f. alkoxylated alcohols;

g. or mixtures thereof;

said terpolymer salt being present in amounts ranging from about 0.1 to about 25 parts by weight per part by weight of the surfactant.

2. A nonphosphorus-containing detergent formulation according to claim 1 wherein the alkyl group of the alkylol radical of the alkylolammonium moiety containing 2 to 6 carbon atoms; the alkyl group of the alkylbenzene sulfonate contains 8 to 20 carbon atoms; the olefin sulfonate is derived from mono-olefins having 10 to 24 carbon atoms; the alkyl group of the alkylsulfonate contains 10 to 24 carbon atoms; the alkanol sulfate is derived from monohydroxy alkanols having 10 to 24 carbon atoms; the alkoxylated alkanol sulfate is derived from monohydroxy alkanols having 8 to 24 carbon atoms which have been alkoxylated with up to wt% of a C, or C alkylene oxide; and the alkoxylated alcohol is derived from monohydroxy alkanols containing 8 to 24 carbon atoms which have been alkoxylated with about 45 wt% to 80 wt% of a C or C alkylene oxide.

3. A nonphosphorus-containing detergent formulation according to claim 1 wherein the alkali metal in each case is sodium or potassium.

4. A nonphosphorus-containing detergent formulation according to claim 1 wherein the alkylolammonium moiety in each case is triethanol ammonium. l i' i 

1. A NONPHOSPHORUS-CONTAINING DETERGENT FORMULATION CONSISTING ESSENTIALLY OF A SURFACTANT AND AN ALKALI METAL, AMMONIUM, OR ALKYLOLAMMONIUM SALT OF WATER-SOLUBLE TERPOLYMER OF ABOUT 10 TO 40 PERCENT BY WEIGHT ALLYL ALCOHOL, ABOUT 1 TO 43 PERCENT BY WEIGHT SULFUR DIOXIDE AND ABOUT 20 TO 83 PERCENT BY WEIGHT ACRYLIC OR METHACRYLIC ACID, PROVIDED THAT THE PARTICULAR PROPORTIONS FALL WITHIN THE SHADED AREA OF THE DIAGRAM ON THE ANNEXED DRAWING; SAID SURFACTANT BEING A. AN ALKALI METAL, AMMONIUM, OR ALKYLOLAMMONIUM ALKYLBENZENE SULFONATE; B. AN ALKALI METAL, AMMONIUM, OR ALKYLOLAMMONIUM OLEFIN SULFONATE; C. AN ALKALI METAL, AMMONIUM, OR ALKYLOLAMMONIUM ALKYLSULFONATE; D. AN ALKALI METAL, AMMONIUM, OR ALKYLOLAMMONIUM ALKANOL SULFATE; E. AN ALKALI METAL, AMMONIUM, OR ALKYLOLAMMONIUM ALKOXYLATED ALKANOL SULFATE; F. ALKOXYLATED ALCOHOLS; G. OR MIXTURES THEREOF; SAID TERPOLYMER SALT BEING PRESENT IN AMOUNTS RANGING FROM ABOUT 0.1 TO ABOUT 25 PARTS BY WEIGHT PER PART BY WEIGHT OF THE SURFACTANT.
 2. A nonphosphorus-containing detergent formulation according to claim 1 wherein the alkyl group of the alkylol radical of the alkylolammonium moiety containing 2 to 6 cArbon atoms; the alkyl group of the alkylbenzene sulfonate contains 8 to 20 carbon atoms; the olefin sulfonate is derived from mono-olefins having 10 to 24 carbon atoms; the alkyl group of the alkylsulfonate contains 10 to 24 carbon atoms; the alkanol sulfate is derived from monohydroxy alkanols having 10 to 24 carbon atoms; the alkoxylated alkanol sulfate is derived from monohydroxy alkanols having 8 to 24 carbon atoms which have been alkoxylated with up to 80 wt% of a C2 or C3 alkylene oxide; and the alkoxylated alcohol is derived from monohydroxy alkanols containing 8 to 24 carbon atoms which have been alkoxylated with about 45 wt% to 80 wt% of a C2 or C3 alkylene oxide.
 3. A nonphosphorus-containing detergent formulation according to claim 1 wherein the alkali metal in each case is sodium or potassium.
 4. A nonphosphorus-containing detergent formulation according to claim 1 wherein the alkylolammonium moiety in each case is triethanol ammonium. 